Hydrolysis of titanium solutions



. Patented June 8, 1943 I -HYDROLYSIS or TITQNIUM SOLUTIONS John Lewis Keats and Henry Moroni Stark, Wilmington, Del., assignors to E. I.-du Pontde Nemours & Company, Wilmington, Del., a corporation of Delaware -No Drawing. Application December 2'1, 1939,

Serial No. 311,104

8 Claims. (CL 23-202) This invention relates to the production j of titanium oxide compounds adapted for ultimate use as pigment substances, and more particularly to*improvements in hydrolysesprocedures commonly used in producing such pigments. More specifically, it relates to a novel method for accelerating the hydroly is of titanium salt solutions, and especially solutions of fate.

-A number of methods for accelerating the hydrolysis of titanium salt solutions embodying the use of varioustypes of seeding or nucleating agents have been already proposed; One such prior process-effects nucleation by employing relatively large amounts (40% on the pigment basis) of raw, untreated TiOg from a previous hydrolysis. Aside from being uneconomical and commercially prohibitive because use ofsuch large quantities of raw pigment precipitate is required, no marked or significantly beneficial results arise from a practice of this type of process. Another titanium sulv titanium salt solution by treating such precipitate with sulfuric acid, and thence employing the resulting seeding material to accelerate hydrolysis of a titanium liquor. v

In a more specificand preferred embodiment, the'invention comprises subjecting a precipitated, raw titanium ,hydrolysate to heat treatment in the presence of an amount of relatively concentrated sulfuric acid insufllcient to effect complete dissolution of said precipitate, and then employing the resulting activated seed material as a nucleating agent to accelerate hydrolysis of a titanium sulfate solution.

In conducting the invention in accordance with trated sulfuric acid sufficient in amount to effect partial dissolution of the raw titanium oxide pi 'ment, but insufficient to'completely solubilize the same. For such purpose, a quantity of acid ranging from substantially 1 mol to 2.5 =mols H2804 per mol of TiO: may be used. Preferably, and to I obtain optimum benefits hereunder, an amount-of drochloric or nitric acid. As a necessary adjunct to its operability, desulfation and removal of H2804 present in the raw precipitate is essential before one can obtain desired peptization. This purification is effected by either washing the a T102 precipitate or neutralizing the same with aseeding agent useful in titanium hydrolysis may H2804 ranging from about 1.3 orv 1.5 to about 2.0

mols of HzsOi per mol of TlOais used. The concentration of the acid, after dilution with any water present in the raw pigment, that is, the

concentrationof the attack acid in contact with.

' the pigment prior to subsequentheatlng, should be in the range of from about 30% to 85% and, preferably, from about 40% to about H2804.

' After mixing or slurrying the raw titanium oxide be obtained from raw, precipitated titanium oxide without resorting to the disadvantageous time and cost-consuming purification operations considered necessary heretofore.

It is among the objects of our invention, therefore, to provide anovel process for attaining these and other advantageous results.- A particular obfrom raw pigment titanium oxide precipitate produced in a previous hydrolysis. Other objects pigment with the requisite quantity andconcentration of acid, the resulting mixture is heated,

for a relatively short periodof time, preferably to a temperature above about ,C., andito near the boiling point of the solution, being held in this temperature range until the appearance of the opaque slurry becomes substantially translucent.

of titanium liquors, especially titanium sulfate.

The amount of activated seed material required for such seeding will be found to be relatively small, and in general may range from about .l,%

, to 20% on the pigment basisa preferred, workand advantages will be apparent from the ensuing description of our invention.

' 'These objects are accomplished in this invening range being from, about 1% to-5% or 10%, 011 the pigment basis. After adding or otherwise incorporating. the seedsuspenslon in the titanium liquor, the resulting nucleated solution is then heated to boiling in accordance with usual and tion which comprises dispersing raw T102 pigment particles arising from the hydrolysis of a .tion' is eil'ected.

normal hydrolysis proceduressu'ch heating being continued until substantially complete precipita- To a more complete understanding of the invention, the following examples are given in illustration, none of which, however, are to be considered as limiting the scope of our invention:"

Example I Anatase raw pigment containing 33% Ti02 on the weight basis and equivalent to 40 parts Ti02' was slurried with 90 parts of concntrated H2804 equivalent to 175" mols H2804 per mol T102, which gave an acidsolution containing about 53% H2804 in contact with the H02. The slurry was heated at 120 C. to 130 C. until it became translucent in appearance. This translucent dispersion was then added to a solution of titanium Example II Seed nuclei were prepared as in Example I by partially dissolving anatase raw pigment in 53% H2804 containing 1.75 mols H2804 per mol Ti02. This seed suspension was added to titanium sulfate solution in an amount equivalent to 0.3% on the pigment basis. The yield after boiling the seeded solution for three hours was 72.0%.

Example III Seed nuclei were prepared by partially dissolving rutile raw pigment prepared by the hydrolysis of TiCl4 solution. The acid solution used in attacking the raw pigment contained 57% H2804 and seed suspension to the amount of 5% on the 'Ii02 basis was added to the titanium sulfate solution. The yield after 3 hours boiling was 57%.

Although specific hydrolysate or raw pigment titanium dioxide precipitates have been used hereinabove as starting materials in the preparation of our novel type of seeding agent, it will be understood that by the term hydrolysate to 35% Ti02, but it is to be understood that any other grade or character of raw pigment may be used in the invention, since it is only necessary that in preparing the reaction mixture the amounts and concentration of the added sulfuric acid be suitably adjusted to produce a mixture in which the ratio of H2804 to Ti02 and the ratio of H2804 to H20 are within the specified ranges; Thus, the invention may be illustrated by one rather extreme modification in which seedcontaining nuclei of very desirable properties is prepared by mixing previously dried and pulverized raw pigment with sulfuric acid of 85% to 95% concentration to give a paste containing about 65% H2804 by weight. This paste is heated at about 180-200" C. until partial attack occurs and the opaque, white mass becomes brown in appearance. The mass is then disintegrated by mixing with hydrolysis solution or with cold water to give a colloidal solution which is quite effective in accelerating hydrolysis when heated under hydrolysis conditions.

As will be evident, the benefits obtainable in this invention are accomplished by using colloidal seed nuclei prepared by dispersing raw titanium oxide pigment particles by means of sulfuric acid itself. The invention thus advantageously eliminates the undesired desulfation of the acid cake which has been required when previous types of hydrolysis seeding agents have been prepared. Furthermore, hydrolysis is readily effected by the use of as little as 1% or even less of the resulting seed material, whereas in prior procedures,

where no seed conditioning is efiected, about 40% is specified. Again, the seed material used in our process is readily available, being obtained from-a normal hydrolysis product, and the sulfuric acid which is employed isusd elsewhere we have reference to precipitates resulting from A the hydrolysis of titanium salt solutions, e. g., the sulfate, chloride, etc. examples of well-known processes for their production including those set out in U, 8. Reissue Patents 18,854, 18,790 or in U. 8. Patent 2,062,133.

Also, though particular temperatures have been specified hereinabove' for effecting desired conditioning of the seed material after treatment with sulfuric acid, these temperatures are not to be considered as critical to the invention. Thus, temperatures to as low as about 80 C. to 90 0.,

provided the time of heating is sufficiently prolonged, may be'used, as may temperatures up to the order of, say, 200 C. Preferably, however, temperatures which substantially approach the boiling point of the attack acid are most advantageously employed.

Again, while the novel seeding agent of our invention is notably useful for accelerating the hydrolysis of titanium sulfate solutions, the same may be used, if desired, as a seedingagent in the hydrolysis of other types of titanium solutions, such as the nitrate, chloride, oxalate, fluoride,

etc. a -1In the above examples, wet anatase raw pigment has been used and to this concentrated in the process in attacking a titaniferous ore such as ilmenite. Thus, no additional chemicals are required in effecting preparation of our seeding agent.

We claim as our invention:

1. A process for producing a nucleating agent useful for accelerating the hydrolysis of a titanium salt solution, comprising subjecting a titanium oxide precipitate obtained from the hydrolysis of a titanium salt solution to treatment with an amount of sulfuric acid sufiicient to partially dissolve said precipitate but insufflcient to completely solubilize the same, and

maintaining the resulting opaque suspension at 7 an elevated temperature until the same becomes substantially translucent to develop its nucleating characteristics.

2. A process for producing a nucleating agent 7 useful in titanium liquor hydrolysis, comprising mixing raw precipitated pigment Ti02 obtained from the hydrolysis of a titanium salt solution with sulfuric acid, and then conditioning the resulting opaque mixture by heating at an elevated. temperature until the same becomes substantially translucent, the ratio of H2804 to Ti02 in said mixture being in excess of molecular proportion but short of an amount of; acid. suilicient to completely solubilize said Ti0 I 3. A process for producing a ilifiicleating agent useful for accelerating the hydrolysis of titanium salt solutions comprising mixing precipitated raw T102 obtained from the hydrolysis of a titanium salt solution in an excess quantity of sulfuric acid, insuflicient to effect complete dissolution of said TiOa, and thence subjecting the resultant opaque mixture to heat treatment at temperatures ranging from about 80 C. to the boiling point of said mixture and until the same becomes substantially translucent.

4. A process for producing a nucleating agent useful for accelerating the hydrolysis of titanium liquors comprising mixing precipitated raw pigment titanium oxide from a previous hydrolysis of a titanium salt solution with an amount of relatively concentrated sulfuric acid, ranging from about 1 mol to 2.5 mols to each mol of T102, and heating the resulting opaque mixture below its boiling point until said mixture becomes substantially translucent.

5. A process for producing a nucleating agent useful for accelerating the hydrolysis of titanium sulfate solutions comprising mixing precipitated titanium oxide obtained from the hydrolysis of a titanium salt solution with sulfuric acid to obtain a mixture containing acid of 30% to 85% concentration and a ratio of 1.3 to 2.0 mols HZSO to each mol of TiOz, and thereafter subjecting the resulting opaque mixture to heat treatment at temperaturesjranging from 90 C. to the boiling point of the acid solution until said mixture becomes substantially translucent.

6. A process for producing a.nucleating agent adapted to accelerate the hydrolysis of a titanium sulfate solution, comprising mixing precipitated titanium oxide obtained from the hydrolysis of a titanium salt solution with an amount of sulfuric acid sufllcient to only partially solubilize said oxide, and then maintaining the resulting opaque mixture at a temperature above about- 100" C. and under its boiling point until said mixture is rendered substantially translucent in appearance.

7. A process for producing a nucleating agent adapted to accelerate the hydrolysis of a titanium sulfate solution, comprising mixing raw anatase precipitate obtained from the hydrolysis of a titanium sulfate solution with an excess quantity of relatively concentrated sulfuric acid but insufllcient to completely solubilize said anatase, and thereupon maintaining the resulting opaque mixture at a temperature above about 100 C. and under its boiling point until said mixture presents a substantially translucent appearance.

8. A process for hydrolyzing titanium sulfate solutions comprising mixing a hydrolyzed, TiOz precipitate obtained from the hydrolysis of a titanium sulfate solution with a quantity of sulfuric acid such that the resultant mixture contains at least one part of H2804 per two parts of H20, and said amount of acid is inzexcess of the molecular proportion of the T102 but insufli- 

